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United States ‘Patent
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3,082,872
Patented Mar. 26, 1963
2
Stage 2
250 ‘g./ t. sodium laurylphosphate
3,082,872
FROTH FLOTATION 0F CRYOLITE
Artur Ernst Heinrich Bergmann, Meggen A.D. Lenne,
Germany, assignor to Klockner-Humholdt-Deutz
Aktiengesellschaft, Koln-Deutz, Germany, a corpora
tion of Germany
No Drawing. Filed May 3, 1961, Ser. No. 107,327
Claims priority, appiication Germany May 6, 1960
4 Claims. (Cl. 209-167)
55 g./t. laurylpyridiniumbromide (cationic collecting
agent)
It is preferable that the sodium lauryl phosphate is
added to the second stage in two portions, of which the
second portion is added toward the end of the second ?o
tation stage. It is also preferable to add the cationic
10 collecting agent at this time. As a rule, it is not neces
My invention relates to a froth ?otation method for
sary to add acid in the second stage, because the addi
cryolite.
tion of acid to the ?rst stage is su?‘icient in most cases
Cryolite deposits generally contain about 80 to 85%
for the second stage also to be acidic. In the example
cryolite, the remainder being ?uorspar, iron spar (sider
described above, the pH value in the second stage in
ite), quartz, sul?des, thomsenolite, pachnolite and 15 creased to about v6.8.
hagemannite.
The ?otation had the following result:
It is an object of my invention to eliminate the just
mentioned impurities by a froth ?otation method.
Cryolite '
Since the ore is often intimately mixed with gangue,
Weight
Percent
the ore must be ground down to minus 100 microns (0.‘1 20
Percent Percent
millimeter).
Output
According to a known method, the ore is ?rst sub
jected to sul?de ?otation, whereafter the cryolite itself
is activated by addition of ‘sodium ?uoride, so that it
Froth products _______________________ __
30. 6
36. 00
14. 0
Concentrate __________________________ . .
69. 4
97. 08
86. 0
100. 0
78. 44
100.0
can be carried off by means of fatty acids or their soaps, 25
after several subsequent purifying stages. This method
has the following disadvantages:
(1) Several subsequent purifying stages are necessary
In another example, the following reagents were con
sumed:
Stage 1
(2) A long froth-forming time and therefore a large
cell volume is necessary, because the major portion of 30
1‘0 kg./t. CuSO4
the ore, cryolite, is ?oated away;
200
t. H2804
(3) Cryolite, enriched in the froth, causes consider
200 g./t. potassium ethyl xanthate (collecting agent)
able di?iculties in the further fabricating processes be
40 g./t. pine oil (frothing agent)
cause such cryolite is no longer wettable.
According to my invention, a considerable improve 35
Stage‘ 2
ment of the ?otation process is achieved by proceeding as
250 g./t. sodium laurylphosphate
follows. The pulp, in acidic condition, is provided with
55 g./t. laurylpyridiniumbromide
copper sulfate or a similar medium and is processed by
means of a collecting agent and a frothing agent, in or
The pH values were similar to those listed in the ?rst
der to ?oat away the major portion of the impurities. 40
The ?rst stage discharge is then ?oated in a second stage
example.
The ?otation had the following result:
by use of a fatty-alcohol-phosphorus acid ester salt, like
wise in an acidic bath, in order to ?oat away the residue
of the impurities. The ?otation is eliected in an acidic
pulp in order to prevent ?oating of the cryolite.
Weight
Cryollte
Percent
45
Percent
In the ?rst stage, the sul?des of the gangue are suffi
Percent
Output
ciently activated by the addition of copper sulfate and
an acid. Conversely, the cryolite is su?iciently passivated
by addition of the copper sulfate. When quartz is pres
ent in the gangue, the method of the invention can be 60
Froth products _______________________ .Concentrate __________________________ ._
17. 1
82. 9
35.10
98. 12
6. 9
93. 1
100. 0
87. 40
100. 0
further improved by adding a cation-active medium, for
example an amine, to the second stage. This has the
advantage of increasing the elimination of quartz.
I claim:
1. A froth ?otation method for recovering cryolite,
comprising acidifying a cryolite ore pulp, said cryolite
The following example relates to an ore containing
on the average ‘80% cryolite, ‘3% ?uorspar, 8% siderite, 55 ore pulp containing impurities comprising sul?des, ?uor
the residue consisting of quartz, sul?des, pachnolite,
spar and siderite, adding in a ?rst stage copper sulfate,
thomsenolite and hagemannite. The ore was ground to
potassium ethyl xanthate and pine oil to ?oat the sul?de
a grain size of minus 100p and was processed in the ?rst
impurities, adding in a second stage sodium laurylphos
?otation stage at ‘250 g. solids per liter. Sulfuric acid
phate to ?oat the remainder of the impurities.
was used to adjust the pH of the pulp to about 5.0. City 60
2. A froth ?otation method for recovering cryolite,
water of Cologne, Germany, having a hardness of 17°
comprising acidifying a cryolite ore pulp, said cryolite
DH was the water used.
The reagents used were as
follows:
ore pulp containing impurities comprising sul?des, ?uor
spar, siderite and quartz, adding in a ?rst stage copper
Stage 1
1O kg./t. CuSO4
300 g./t. H2504
200 g./t. potassium ethyl xanthate (collecting agent)
40 g./ t. pine oil (frothing agent)
sulfate, potassium ethyl xanthate and pine oil to ?oat the
sul?de impurities, adding in a second stage sodium lauryl
phosphate and laurylpyridiniumbromide to ?oat the re
mainder of the impurities.
3. A froth ?otation method for recovering cryolite,
comprising acidifying a cryolite pulp containing impuri
The ?rst stage concentrate was supplied to a second 70 ties comprising sul?des, ?uorspar and siderite to a pH of
?otation stage in which the following reagents were con
5, adding in a ?rst stage copper sulfate, potassium ethyl
sumed:
xanthate and pine oil to ?oat the sul?de impurities, add
3,082,872
4
ing in a second stage sodium laurylphosphate to ?oat the
remainder of the impurities.
4. A froth ?otation method for recovering cryolite,
References Cited in the ?le of this patent
UNITED STATES PATENTS
comprising acidifying a cryolite pulp containing impuri
ties comprising sul?des, ?uorspar, siderite and quartz to 5
a pH of '5, adding in a ?rst stage copper sulfate, potas
sium ethyl xanthate and pine oil to ?oat the sul?de im
purities, adding in a second stage sodium laurylphosphate
and laurylpyridiniumbromide to ?oat the remainder of
the impurities, whereby the major portion of the cryolite 10
remains in the concentrate,
'
1,966,649
Schranz
2,132,902
2,759,962
2,965,23 l
Lenher ______________ __ Oct. 111,
Zenftman __________ __ Aug. 21,
Goldenhar __________ __ Dec. 20,
Hazen ______________ _.. June 5,
3,037,627
July 17, 1934
1938
1956
1960
1962
FOREIGN PATENTS
557,804
Germany ____________ __ Aug. 27, 1937